Antimicrobial detergent composition containing aminopolyureylene resin

ABSTRACT

Detergent compositions comprising a mixture of 2-99 percent by weight of a water-soluble organic detergent, 0.05 to 5 percent by weight of an aminopolyureylene resin having a molecular weight in the range of about 300 to 100,000 and 0.05 to 5 percent by weight of a water-soluble or water-insoluble antimicrobial agent. Preferred compositions contain 10 to 40 percent by weight of detergent, 0.5 to 3.5 percent by weight of resin, 0.1 to 3 percent by weight of antimicrobial agent, and water.

I United States Patent 1191 [11] 3,875,071

Grand Apr. 1, 1975 ANTIMICROBIAL DETERGENT 3311.594 3/1967 Earle 260/775CO O CONTAINING 3,489,686 1/1970 Parrun 252/106 3.506.720 4/1970 Modelet a1 252/106 AMINOPOLYUREYLENE RESIN 3,668,135 6/1972 Nosler et a1.252/106 [75] Inventor: Paul Sheldon Grand, South Bound 3.681.249 8/1972Traber ct a1. 252/106 B k NJ 3.725.547 4/1973 Kooistra 252/106 [73]Assignee: colgf'te'palmolive Company New Primary Eraminer-Leland A.Sebastian York Assist/111! E.\an1ine/'E. A. Miller 22 i 22 1972Attorney, Agent, or Firn1Richard N. Miller; Ronald S. Cornell; HerbertS. Sylvester [21] Appl. No.: 308,884

Related US. Application Data 1 1 ABSTRACT [62] Division of SCI. N6.90154. Nov. 16. 1970. Put. NO. Detergent Compositions Comprising amixture Of 3,726,815. 2-9992 by weight of a water-soluble organicdetergent, 0.05 to 5 percent by weight of an aminopolyureylene [52] US.Cl. 252/106, 252/544 resin halving :1 molecular weight in the range ofabout [51] Int. Cl Clld 3/48 300 t 0 00 d 0- 5 to 5 p nt y ig t of a[58] Field of Sear h 352/1()6 544 water-soluble or water-insolubleantimicrobial agent. Preferred compositions contain 10 to 40 percent by[56] References Cited weight of detergent 0.5 to 3.5 percent by weightof UNITED STATES PATENTS resin. 0.1 to 3 percent by weight ofantimicrobial 3,156,672 11/1964 vim def Kerk (H211 260/775 and 3.240.6643/1966 Earle 162/164 9 Claims, No Drawings ANTIMICROBIAL DETERGENTCOMPOSITION CONTAINING AMINOPOLYUREYLENE RESIN This is a divisional, ofapplication Ser, No. 90,154

filed Nov. 16, 1970, now US. Pat. No. 3,726,815.

The invention relates to improved compositions comprising awater-soluble and/or water-insoluble active material having the capacityto impart a residual characteristic to surfaces treated therewith suchas antibacterial compounds, tarnish inhibitors, ultra-violet absorbers,fluorescent brighteners, bluing agents and skin treating materials andan aminopolyureylene (APU) resin in an amount effective to enhance theeffects of the active materials. The APU resins appear to enhance thedeposition and/or retention of thewater-soluble and waterinsolubleactive substances on the surfaces contacted therewith.

The capacity of the APU resin to improve the effectiveness of the activematerials on surfaces contacted therewith surprisingly is maintained inthe presence of water-soluble organic detergents and, therefore,detergent compositions containing the mixture of active material and APUresin represent preferred embodiments. Such detergent compositionsinclude dishwashing detergents, shampoos, laundry detergents,hardsurface cleaners and toilet bars. The effectiveness of the APUresins in the presence of minor and major amounts of watersolubleorganic detergents is surprising because the effectiveness of the activematerials is due to the deposition and/or retention of the activematerials on surfaces contacted therewith and detergents normally tendto minimize deposition and retention of such materials on the washedsurfaces. Thus, usually only a small percentage of the active materialsin a detergent composition is actually retained ona particular surfaceor substrate after washing and, optionally, rinsing. Accordingly, toachieve a particular level of activity, the concentrations of activematerial must be increasedwith an attendant increase in cost when usedas a component in a detergent composition.

While the mechanism by which the improved effects are obtained is notunderstood, it appears that the APU resin may unite either with theactive material or'thecontacted surface to increase the affinity of theactive material for the surface. In many cases, an increase in theweight of active material retained by the surface has beenquantitatively verified. However, no absolute mechanism has been definedand the invention is not limited to any particular theory.

Generally, the improved compositions of this invention consistessentially of a mixture of i an aminopolyureylene resin having amolecular weight in the range of about 300 to 100,000 and awater-soluble or water-insoluble active material having the capacity toimpart a residual property to surfaces treated therewith and selectedfrom the group consisting of (A) antibacterial compounds, (B) tarnishinhibitors, (C) ultraviolet absorbers, (D) optical brighteners, (E)bluing agents and (F) skin-treating compounds, the weight ratio of resinto active material being effective to improve the effects of the activematerial and selected from the range of 1:1 to :1 preferably 1:1 to 5:1.Preferred compositions are detergent compositions comprising 2% to 99%by weight of a water-soluble, organic detergent, 0.05% to 5% by weightof aminopolyureylene resin and about 0.05 to 5% by weight of activematerial.

Also, within the scope of the invention is a method for improving theeffectiveness of active materials on surfaces contacted therewith whichcomprises contacting the surface with a water solution or dispersion of5 the active material and an effective amount of the aminopolyureyleneresin sufficient to improve the effect of the active material retainedon the treated surface after the contacting solution is removed.

The APU resins suitable for use in the described compositions and methodhave a molecular weight. in the range of about 300 to 100,000 and arecharacterized by the following repeating unit: -[-(CI-I ),,X- (CH),,NHC(Y)NH+ wherein X is NH, NC to C alkyl, 7

en ca 4.2 2;; \CH2 CH2,

Generally, the number of repeating units in the resin will be sufficientto yield a polymer having a molecular weight in the range of about 300to 100,000. Preferred APU resins have an average molecular weight in therange of 1,000 to 20,000 and a particularly preferred resin is thereaction product of equimolar quantities of N-methyl,bis(3-amino-propyl) amine and urea having a molecular weight of about4,300.

The molecular weight of the APU resins is based upon aqueous gelpermeation chromatographic analysis. The separation is carried out inoxalic acid solution, adjusted to pH 3.5, on three Corningcontrolled-pore glass columns (nominal pore sizes 175,125 and 75A) inseries. Detection is by differential refractometer. Reference compoundsare dextran polysaccharides of molecular weights of 150,000, 110,000,40,000, 20,000 and 10,000 and sucrose and galactose.

The APU resins which can be used in the compositions of this inventionare prepared by reacting, for example, 145 grams of N-methyl bis(3-aminopropyl) amine (1.0 mole) and grams of urea (1.0 mole) in a3-necked flask equipped with a therometer, mechanical stirrer,condenser, and nitrogen sparge tube. Nitrogen is bubbled slowly throughthe solution throughout the course of the reaction. The solution isheated to piperazine or N,N-di (2-aminoethyl) piperazine with urea orthiourea. The'N-C, to C alkyl analogues are prepared by reacting N-C toC alkyl bis(3- aminopropyl) amine or N-C to C alkyl bis(2- aminoethyl)amine with urea or thiourea. Additional analogues are prepared by thefollowing reactions:

CH3 Resin A I epichloronydrin ll analogues GH -220x 01 p11 P 3 1 q+analogues Na0H -9 F analogues CH CH-Cl'l CHQ CHCHQCI. 2 2

till

CH 3 analogues 9 3 M H 0 N'*' analogues l 2 "Mi-3 caggn-cngon 0 OH eRuin A dimethyl sulfate rr' analogues The preparation of theremaininganalogues is well within the skill of the art following the abovetechniques.

The active materials which are potentiated by the APU resin are wellknown and have been used for treating surfaces and substrates to impartcertain residual characteristics to the contacted surfaces. The treatedsurfaces or substrates include proteinaceous materials such as hair andskin, textiles such as cotton, rayon and synthetic fibers, andporcelain, wood, plastic and metal. Such active materials may bewater-soluble such as cetyl dimethyl benzyl ammonium bromide and gelatinor water-insoluble such as zinc Z-pyridinethioll-oxide and opticalbrighteners. To facilitate activity and utility, the water-insolublematerials are usually in the form of finely divided particles having adiameter in the range of about 0.5 to 50 microns. Suitable activematerials include antibacterial compounds, tarnish inhibitors,ultra-violet absorbers, optical brighteners, bluing agents and skintreating materials such as hydrolyzed proteins, silicones andpolyacrylamides.

Antibacterial compounds which may be used in the compositions includewater-soluble and waterinsoluble salts of Z-pyridinethiol-l-oxide,substituted salicylanilides, substituted carbanilides, halogenatedbisphenols, mono-higher alkyl quartemary ammonium salts, and5,7diiodo-8-hydroxyquinoline.

Preferred antibacterial compounds include the waterinsoluble salts,e.g., zinc, cadmium, zirconium,tin and aluminum, and water-solublesalts, e.g., sodium and potassium, of Z-pyridinethiol-l-oxide which hasthe following structural formula in tautomeric form.

The zinc and sodium salts of Z-pyridinethiol-l-oxide are particularlypreferred.

Other suitable antibacterial compounds are the substituted bisphenolshaving the formula wherein Y is hydrogen, halogen, or trifluoromethyland- Z is hydrogen or halogen. Among the suitable salicylanilides are3,4',5 tribromosalicylanilide; 5-

bromosalicyl 3,5 di(trifluoromethyl)anlide; 5 chlorosalicyl 3,5di(trifluoromethyl)anlide; 5 3,5 di(trifluoromethyl)anlide; 3,5-dichlorosalicyl 3,4 dichloroanilide; and 5 chlorosalicyl 3trifluoromethyl 4 chloroanilide, These and other useful salicylanilidesare disclosed in U.S. Pat. No. 2,703,332.

Satisfactory substituted carbanilides have the following generalstructure Y O Y H Q- NH. 0- NH- wherein Y is hydrogen, halogen, ortrifluoromethyl, W is halogen or ethoxy, and W is hydrogen or halogen.

Included among the suitable carbanilides are 3,4,4 trichlorocarbanilide;4,4-trifluoromethyl 3'4,4' trichlorocarbanilide; 3,3 bis(trifluoromethyl4 ethoxy 4 chlorocarbanilide; and 3,5 bis(trifluoromethyl) 4'chlorocarbanilide.

wherein R, is C, to C alkyl, R and R are each C, C, alkyl, R is C, Calkyl or benzyl and A is an anion selected from the group consisting ofchlorine, bromine, iodine, and methosulfate. A preferred compound iscetyl trimethyl ammonium bromide.

Additional useful antimicrobial compounds include 5,7-diiodo-8-hydroxyquinoline, 1,6- di(4'chlorophenyl-diguanado) hexane, and 5-chloro-2(2,4-dichlorophenoxy)phenol, C to C isoquinolinium halides, suchas'lauryl isoquinolinium bromide, and C C alkyl pyridinium halide.

The tarnish inhibitors potentiated by APU resins include, for example,benzotriazole and ethylenethiourea.

Ultraviolet absorbers potentiated by APU resins have the structuralformula where X, Y, and Z are selected from the group consisting ofhydrogen, hydroxy, C, to C alkoxy and carboxy, at least one of said X,Y, and Z being oxy. Preferred compounds include2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-methoxy-2-carboxybenzophenone.

The optical or fluoroescent brightener active materials which arepotentiated by the APU resins are selected from the group consisting ofstilbene disulfonates, quatemized aminoalkyl substituted phenylsulfonamides of aryl pyrazolines, substituted styrylnaphth o);- azoles,and substituted aminocoumarins.

Suitable stilbene disulfonate fluorescent brighteners have the formula CN\ N C n c-NHQ CH=CH- Ant-c =N \N=C l I x so r: 0 K

ea er- 0H CHZCHEOH 6 Suitable compounds are disodium 4,4 bis[4-anilino-6- methoxyanilino-s-triazin-Zyl amino]-2 ,2' stilbenedisulfonate and disodium 4,4 bis (4,6 dianilino-s-triazin-2yl amin'o)2,2 stilbene-disulfonte.

Suitable quatemized aminoalkyl substituted phenyl sulfonamides of arylpyrazoline have the following formula:

X HC N wherein X is hydrogen, phenyl, or halogenated phenyl with notmore than one X being hydrogen and Y is a quaternized ia cn= cn- Qwherein A and B are different and represent oxygen and nitrogen, and Rrepresents individually hydrogen, alkyl groups having 1 to 6 carbonatoms, chlorine or fluorine. A preferred oxazole brightener is 2-strylnaphth (1,2-d) oxazole.

Additional fluorescent brighteners potentiated by APU resin are thewater-soluble substituted aminocoumarins having the following structuralformula:

H R\ i) ,=:0 R/ Y wherein R is hydrogen or C, C alkyl. A preferredcompound is 4 methyl, 7 dimethyl amino coumarin.

A bluing material which is potentiated by APU resin is ultramarine blue.This is a well-known blue pigment occurring naturally as mineral thelapis lazuli. It can be.

made, for example, by igniting a mixture of kaolin, sodium carbonate orsulfate, sulfur, and carbon. It is insoluble in water and is stable whenin contact with wherein X is OH, DIE-Q CH ----CH' N/ 2 0 or Nii .ocn andY is Nit-Q n(c r cn oH) or @ocn bleaching agents, alkali, and light.Details for synthetic ultramarines are given in the text fUltramarines,Their' History and Characteristics, Reckitts (Colours) Ltd., Hull,England. Preferred -are micropulverized, syntheticultramarine blues,particularly grades-RS4g-RS8 provided by Reckitts. The pigment is in theform of par-1 ticles substantially all of which exhibit a diameter ofless than about 0.05 millimeter, and is characterized by the ability toimpart a faint blue visible shade to fabrics treated therewith withoutstaining such fabrics when used at recommended concentration andfashion, being generally considered to be non-substantive, or at leastnon-accumulative, on fabrics. r

The skin-treating materials which are teins. Such proteins aresubstantive to the hair and skin in the presence of detergents. Suitableproteins are watersoluble polypeptides, having a molecular weight in therange of about 120 (amino acid to about 20,000, preferably from about800 to 12,000. Such polypeptides are obtained by hydrolysis of proteinrna terials such as hides, gelatinjcollagen, and the like, with collagenprotein being preferred, using wellknown processes. During hydrolysisthe protein materials are gradually broken down into their constituentpolypeptides and amino acids by prolonged heating with acids, e.g.,sulfuric acid, or alkalis, e.g., sodium hydroxide, or treatment withenzymes, e.g., peptidases. First, high molecular weight polypeptides areformed, and as hydrolysis proceeds these are converted progressively tosimpler and simpler polypeptides, to tripeptides, dipeptides, andfinally to amino acids. It is'obvious that the polypeptides derived fromproteins are complex mixtures. The preferred hydrolysates are ob;tained. from boneor skin-derived collagen protein by enzymatichydrolysis and are sold under the trade;

ionic, polar nonionic, and cationic detergents, and mixtures of two ormore of the foregoing detergents.

The anionic surface-active agents include those surfaceactive ordetergent compounds which contain an.

organic hydrophobic group containing generally 8 to 26 carbon atoms andpreferably .10 to 18 carbon atoms in their molecular structure, and atleast one watersolubilizing group selected from the group of sulfonate,sulfate, carboxylate, phosphonate and phosphate so as to form awater-soluble detergent.

enhanced by the APU resins are the water-soluble, substantive pro- 8tures derived from coconut oil and tallow, for example, sodium coconutsoap and potassium tallow soap.

The anionic class of detergents also include the water-soluble sulfatedand sulfonated synthetic detergents having an alkyl radical of 8 to 26,and preferably 'as the higher akyl ber'izene sulfonates containing fromto 16 carbon atoms in the higher alkyl group in a straight or branchedchain, for example, the sodium, potassium, and ammonium salts of higheralkyl benzene sulfonates, higher alkyl toluene'sulfonates, higher alkylphenol sulfonates and higher naphthalene sulfonates, A preferredsulfonate is linear alkyl benzene sul fonate having a high content of 3-(or higher)phenyl isomers and a correspondingly low content (well below50 percent) of 2- (or .lower) phenyl isomers, that is, wherein thebenzene ring is preferably attached in large part at the 3 orhigher'(for example, 4, 5, 6 or 7) position of the alkyl group and thecontent of the isomers in which the benzene ring is attached in the 2 or1' position is correspondingly low. Particularly preferred materials areset forth in US. Pat. No. 3,320,174.

Other suitable anionic detergents are the olefin sulfonates, includinglong-chain alkene sulfonates, longchain hydroxyalkane sulfonates ormixtures'of alkene sulfonates and hydroxylalkane sulfonates. Theseolefin sulfonate detergents may be prepared in a known manner by thereaction of 80;, with long-chain olefins containing 8 to 25, preferably12 to 21 carbon atoms and having the formula RCH=CHR where R is a higheralkyl group of 6 to 23 carbons and R is an alkyl group of l to 17carbons or hydrogen to form a mixture of sultones and alkene sulfonicacids which is then treated to convert the sultones to sulfonates. Otherexamples of sulfate or sulfonate detergents are paraffin sulfonates'containing about 10 to 20 and preferably about 15 to 20 carbon atoms,for example, the primary paraffin sulfonates arev made by reactinglong-chain alpha olefins andbisulfites and paraffin sulfonates havingthe sulfo-j nated group distributed along-the paraffin chain as shown inUS. Pat. Nos; 2,503,280; 2,507,088;

3,260,741 3,372, 188; and German Patent 735,096; so-

dium and potassium sulfates of higher alcohols containing 8 to 18 carbonatoms such as sodium lauryl sulfate and sodium tallow alcohol sulfate;sodium and potas: sium salts of a-sulfofatty acid esters containingabout 10m 20 carbon atoms in the acyl group, for example, methyla-sulfomyristate and methyl a-sulfotallowate, animoniumsulfatesof monoordi-glycerides of higher (C C fatty acids, for example, stearicmonoglyceride monosulfate; sodium and alkylolammonium salts of alkylpolyethenoxy ether sulfates produced by condensing l to 5 moles ofethylene oxide with one mole of higher (C -C alcohol; sodium higheralkyl (C Examples of suitable anionic detergents which fall within thescope of the anionic detergent class'in'cl'ude the water-soluble salts,for example, the sodium, ammonium, and alkylolammonium salts, of higherfatty acids or resin salts containing about 8 to 20 carbon atoms,preferably 10 to 18 carbon atoms. Suitable fatty acids can be obtainedfrom oils and waxes of animal or vegetable origin, for example, tal'low,grease, coconut oil, tall oil and mixtures thereof. Particularly usefulare the sodium and potassium salts of the fatty acid mix- C glycerylether sulfonates; and sodium or potassium alkyl phenol pplyethenoxy ethersulfates with about 1 to 6 oxyethylene groups per molecule and in whichthe alkyl radicals contain about 8 to about 12 carbon atoms.

The suitable anionic detergents include also the C to C acylsarcosinates (for example, sodium lauroyl sarcosinate), sodium andpotassiumsalts of the reaction product of higher fatty acids containing8 to 18 carbon atoms in the molecule esterified with isethionic acid,

and sodium and potassium salts of the C to C acyl N- methyl taurides,for example, sodium cocoyl methyl taurate and potassium stearoyl methyltaurate.

Anionic phosphate surfactants in which the anionic solubilizing groupattached to the hydrophobic group is an oxyacid of phosphorous are alsouseful in the detergent compositions. Suitable phosphate surfactants arethe sodium, potassium, and ammonium alkyl phosphate esters such as (R-O)PO M and ROPO M in which R represents an alkyl chain containing fromabout 8 to 20 carbon atoms or an alkyl phenyl group having 8 to 20carbon atoms and M represents a soluble cation. The compounds formed byincluding about 1 to 40 moles of ethylene oxide in the foregoing esters,for example, [R-O(EtO)n] PO M, are also satisfactory.

The particular anionic detergent salt will be suitably selected,depending upon the particular formulation and the proportions therein.Suitable salts include the ammonium, substituted ammonium (mono-, di-,and triethanolammonium), alkali metal (such as sodium and potassium) andalkaline earth metal (such as calcium and magnesium) salts. Preferredsalts are the ammonium, triethanolammonium, sodium, and potassium saltsof the higher alkyl sulfates and the C to C acyl sarcosinates.

The nonionic synthetic organic detergents are generally the condensationproduct of an organic aliphatic or alkyl aromatic hydrophobic compoundand hydrophilic ethylene oxide groups. Practically any hydrophobiccompound having a carboxy, hydroxy, amido, or amino group with a freehydrogen attached to the nitrogen can be condensed with ethylene oxideor with the polyhydration product thereof, polyethylene glycol, to forma nonionic detergent. Further, the length of the polyetheneoxy chain canbe adjusted to achieve the desired balance between the hydrophobic andhydrophilic elements.

The nonionic detergents include the polyethylene oxide condensate of onemole of alkyl phenol containing from about 6 to 12 carbon atoms in astraightor branched-chain configuration with about to 30 moles ofethylene oxide, for example, nonyl phenol condensed with 9 moles ofethylene oxide, dodecyl phenol condensed with 15 moles of ethylene anddinonyl phenol condensed with 15 moles of ethylene oxide. Condensationproducts of the corresponding alkyl thiophenols with 5 to 30 moles ofethylene oxide are also suitable.

Still other suitable nonionics are the polyoxyethylene polyoxypropyleneadducts of l-butanol. The hydrophobe of these anionics has a minimummolecular weight of 1,000 and consists of an aliphatic monohydricalcohol containing from 1 to 8 carbon atoms to which is attached aheteric chain of oxyethylene and oxypropylene. The weight ratio ofoxypropylene to oxyethylene covers the range of 95:5 to 85:15. Attachedto this is the hydrophilic polyoxyethylene chain which is from 44.4 to54.6 of the total molecular weight.

Also included in the nonionic detergent class are the condensationproducts of a higher alcohol containing about 8 to 18 carbon atoms in astraight or branchedchain configuration condensed with about 5 to 30moles of ethylene oxide. for example, lauryl-myristyl alcohol condensedwith about 16 moles of ethylene oxide.

A particularly useful group of nonionics is marketed under the tradename Pluronics. The compounds are formed by condensing ethylene oxidewith a hydrophobic base formed by the condensation of propylene oxidewith propylene glycol. The molecular weight of the hydrophobic portionof the molecule is of the order of 950 to 4,000 and preferably 1,200 to2,500. The addition of polyoxyethylene radicals to the hydrophobicportion tends to increase the solubility of the molecule as a whole. Themolecular weight of the block polymers varies from 1,000 to 15,000, andthe polyethylene oxide content may comprise 20 to 80 percent by weight.

Zwitterionic detergents such as the betaines and sulfobetaines havingthe following formula are also useful:

wherein R is an alkyl group containing about 8 to 18 carbon atoms, R andR are each an alkylene or hydroxyalkylene group containing about 1 to 4carbon atoms, R is an alkylene or hydroxyalkylene group containing 1 to4 carbon atoms, and X is C or 8:0. The alkyl group can contain one ormore intermediate linkages such as amido, ether, or polyether linkagesor nonfunctional substituents such as hydroxyl or halogen which do notsubstantially affect the hydrophobic character of the group. When X isC, the detergent is called a betaine; and when X is 5:0, the detergentis called a sulfobetaine or sultaine. Preferred betaine and sulfobetainedetergents are l-(lauryl dimethylammonio) acetate, l-(myristyldimethylammonio) propane-3- sulfonate, and l-( myristyldimethylammonio)-2- hydroxy-propane-3-sulfonate.

The polar nonionic detergents are those in which the hydrophilic groupcontains a semi-polar bond directly between two atoms, for example, N O,P 0, As O, and S *'O. There is charge separation between the twodirectly bonded atoms, but the detergent molecule bears no net chargeand does not dissociate into ions.

The polar nonionic detergents of this invention include open-chainaliphatic amide oxides of the general formula R R R N O. For the purposeof this invention R is an alkyl, alkenyl, or monohydroxyalkyl radicalhaving about 10 to 16 carbon atoms, R and R are each selected from thegroup consisting of methyl, ethyl, propyl, ethanol, and propanolradicals.

Other operable polar nonionic detergents are the openchain aliphaticphosphine oxides having the general formula R R R P 0 wherein R is analkyl, alkenyl, or monohydroxyalkyl radical ranging in chain length from10 to 18 carbon atoms, and R and R are each alkyl and monohydroxyalkylradicals containing from 1 to 3 carbon atoms.

Examples of suitable ampholytic detergents include the alkylbeta-aminopropionates, RN(H)C H COOM; the alkyl betaiminodipropionates,RN(C H COOM) the alkyl and hydroxy alkyl taurinates, RN(CH )C H SO M;and the long-chain imidazole derivatives having the following formulas:

wherein R is an acyclic group of about 7 to 17 carbon atoms, W isselected from the group of R OH, R COOM, and R OR COOM, Y is selectedfrom the group consisting of OH,R OSO ,R is an alkylene orhydroxyalkylene group containing 1 to 4 carbon atoms, R, is selectedfrom the group consisting of alkyl, alkyl aryl and fatty acyl glyceridegroups having 6 to 18 carbon atoms in the alkyl or an acyl group; and Mis a water-soluble cation, for example, sodium, potassium, ammonium, foralkylolammonium.

Formula I detergents are disclosed in Volume II of Surface Active Agentsand Detergents and Formula 11 detergents are described in US. Pat. No.2,773,068; US. Pat. No. 2,781,354; and US. Pat. No. 2,781,357. Theacyclic groups may be derived from coconut oil fatty acids (a mixture offatty acids containing 8 to 18 carbon atoms), lauric fatty acid, andoleic fatty acid, and the preferred groups are C to C alkyl groups.Preferred detergents are sodium N-lauryl betaaminopropionate, disodiumN-lauryl iminodipropionate, and the disodium salt of2-lauryl-cycloimidium 1- hydroxyl, l-ethoxyethanoic acid, l-ethanoicacid.

Cationic surface active agents may also be employed. Such agents arethose surface active detergent compounds which contain an organichydrophobic group and a cationic solubilizing group. Typical cationicsolubilizing groups are amine and quaternary groups.

Examples of suitable synthetic cationic detergents are normal primaryamines RNl-l wherein R is C to C; the diamines such as those of the typeRNHCJ-LNH wherein R is an alkyl group of about 12 to 22 carbon atoms,such as N-Z-aminoethyl stearyl amine and N-Z-aminoethyl myristyl amine;amidelinked amines such as those of the type R CONHC H NH wherein R isan alkyl group of 8 to 20 carbon atoms, such as N-2-amino ethylstearylamide and N-amino ethylmyristyl amide; quaternary ammonium compoundswherein typically one of the groups linked to the nitrogen atom is analkyl group of about 8 to 22 carbon atoms and three of the groups linkedto the nitrogen atom are alkyl groups which contain 1 to 3 carbon atoms,including alkyl groups bearing inert substituents, such as phenylgroups, and there is present an anion such as halogen, acetate,methosulfate, etc. The alkyl group may contain intermediate linkagessuch as amide which do not substantially affect the hydrophobiccharacter of the group, for example, stearyl amido propyl quaternaryammonium chloride. Typical quaternary ammonium detergents areethyl-dimethylstearyl ammonium chloride, benzyl-dimethylstearyl ammoniumchloride, trimethyl-stearyl ammonium chloride, trimethyl-cetyl ammoniumbromide, dimethyl-ethyl-lauryl ammonium chloride,dimethyl-propylmyristyl ammonium chloride, and the correspondingmethosulfates and acetates.

Preferred detergent compositions of this invention are the liquid,antimicrobial shampoo compositions suitable for washing the hair andscalp. Such compositions consist essentially of about 10 to 40 percentby weight of a detergent selected from the group consisting of non-soapanionic, amphoteric, and zwitterionic detergents from 0.1 -to 3 percentby weight of watersoluble or water-insoluble particulate antimicrobialactive material, 0.5 to 3.5 percent of aminopolyureylene resin, and thebalance primarly water. The shampoo compositions may also include minoramounts of ethanol or isopropanol perfume, color, stearate opacifyingagents, ethylene diamine tetracetate or citrate sequestering agents,thickening agents, and fatty acid alkylolamide foam boosters.

Other detergent compositions falling within the scope of the inventionare the heavy-duty laundering compositions containing APU polymers andat least one of the active materials potentiated by thepolaminopolyureylene resins, such as antibacterials, fluorescentbrighteners, and bluing agents. Such compositions generally consistessentially of about 8 to 40 percent by weight of non-soap anionic ornonionic detergent, about 0.1 to 3 percent by weight of active material,about 0.5 to 3.5 percent by weight of APU resin and the balancewater-soluble inorganic or organic builder salt. Suitable buildersinclude sodium sulfate, sodium carbonate, and sodium nitrilotriacetateas well as the corresponding potassium compounds. Other compositions aresodium carboxymethylcellulose, polyvinylalcohol, perfume, color, etc.

The foregoing laundering detergents may also be prepared in liquid form.Suitable liquids consist essentially of about 5 to 20 percent by weightof non-soap anionic or nonionic detergent, 10 to 25 percent by weight ofpotassium pyrophosphate, sodium silicate or sodium nitrilotriacetate, 4to 12 percent by weight of sodium or potassium xylene ortoluenesulfonate, 0.1 to 3.0 percent by weight of active material, 0.5to 3.5 percent by weight of APU resin, and the balance primarily water.Suitable additives which may be added are sodium carboxymethylcellulose,thickeners, color, and perfume.

In bar form, the detergent material may be soap, anionic, amphoteric,nonionic or mixtures of the foregoing detergents. In addition to theusual proportions of APU resin and active material, the bars may includecolor, perfume, free fatty acids, sodium chloride, and fatty acidalkanolamide suds builders.

Each of the foregoing detergent compositions can be prepared by methodswell known in the art. For example, shampoos and built liquid detergentsare prepared by mixing, and particulate laundering detergents areprepared by mixing, chemical drying or spray drying.

The ability of the APU resins to potentiate the deposition of thewater-insoluble materials which function as antibacterial agents ontoproteinaceous substrates, such as hair and skin, is demonstrated in thefollowing radioactive substantivity test. Substantivity is determined bystirring a 1.27-centimeter diameter circular gelatin disk weighing about40 milligrams for about five minutes in 10 grams of an aqueous mediumcontaining a known concentration of radioactive tagged material such aszinc Z-pyridinethiol-l-oxide, rinsing the disk five times in 10milliliters of water, drying, and measuring the radiation emission withthe aid of a radiation detector. The absolute degree of deposition ofthe material is determined by comparing the observed counts with thecounts emitted by a known weight of the radioactive material. The effectof APU resin on deposition can be readily ascertained by repeating thetest with a known weight of APU present. Similarly, the effect ofdetergents can be quantitatively measured by including detergents in thetest composition.

The following examples are illustrative of the compositions fallingwithin the scope of this invention.

EXAMPLE 1 An aqueous dispersion of zinc 2-pyridinethiol-loxide isprepared by dispersing 0.04 grams of radioactive zincZ-pyridinethiol-l-oxide containing zinc 65 in one gram of water. Theresultant aqueous dispersion is diluted with 8.96 grams of water withagitation, and the substantivity of the diluted dispersion is determinedusing the foregoing substantivity procedure. The results of theevaluation indicate 40.9 micrograms of zinc-2-pyridinethiol-l-oxide aredeposited on the disk from the aqueous mixture containing 0.4 percent byweight of the Z-pyridinethiol-l-oxide. When the foregoing experiment isrepeated in the presence of an amino polyureylene resin (Resin A) havinga molecular weight of about 4,300 and the repeating unit (CI-l N(CH)(C1-1 N(H)C(O)N(1l)-, 122 micrograms of zinc 2-pyridinethiol-l-oxideare deposited on the disk at a concentration of 0.5 percent of saidresin in the aqueous test dispersion. Thus, the presence of 0.5 percentof APU resin results in a 200 percent increase in the deposition ofzinc-2-pyridinethiol-l-oxide from an aqueous medium.

Use of a resin having a molecular weight of about 5,600 andN,N'-di(3-aminopropyl) piperazine as the repeating unit in the foregoingtest yields comparable results.

EXAMPLE 2 When the procedure of Example 1 is repeated using an aqueoussolution of 0.25 percent by weight of radioactive (C-14) cetyltrimethylammonium bromide (CTAB) at pH 4.5 as the test medium, 294micrograms of CTAB are deposited on the gelatin disk. Repetition of thistest in the presence of 0.75 percent by weight of the APU resin used inExample 1 results in the deposition of 679 micrograms of CTAB, anincrease in deposition of about 130 percent. When the pH of the testsolution is increased to 8.5, a deposition of 259 micrograms of CTAB isobtained in the absence of APU resin and a deposition of 734 microgramsis obtained in the presence of 3 percent by weight of the APU resin ofExample 1. Thus, a 180 percent increase in deposition of CTAB is notedat pH 8.5.

EXAMPLE 3 Example 2 is repeated with the exception that a percentaqueous ethanol mixture is substituted for water in the test solutionand the pH is adjusted to 6.5. A deposition value of 202 micrograms ofCTAB is noted in the absence of APU resin, and a deposition value of 643micrograms of CTAB is noted in the presence of 0.73 percent by weight ofthe APU resin of Example This represents an increase in deposition ofabout 220 percent. For comparison, only 227 micrograms of CTAB aredeposited when the concentration of CTAB in the test solution isincreased to 1 percent by weight. Thus, the APU resin is significantlymore effective in enhancing deposition than an increase in the CTABconcentration from 0.25 to 1 percent, a 300 percent increase.

EXAMPLE 4 When the procedure of Example 1 is repeated using a 0.5percent-by-weight aqueous alcoholic dispersion of radioactive (C-l4)bis(3,5,6 trichloro-2- hydroxyphenyl) methane as the test solution, theradioactivity of the gelatin disk averages 2,100 counts per minute(cpm.) Repetition of the test in the presence of 1.25% concentration ofthe APU resin of Example 1 results in an average radioactivity of 13,200cpm. Thus, the presence ot the APU resin increases the deposition of theantimicrobial compound by about 500%. Substantially similar results arenoted when either lamb skin or human callus tissue is substituted forthe gelatin disk in the foregoing experiment.

The APU resin of Example 1 can be replaced by either a resin having amolecular weight of about 4,600 and the repeating unit +Cl-l N (Cl-1(CI-1 NH- C(O)NH-lor a resin having a molecular weight of about 6,700and the repeating unit with substantially similar results. Similarly,the substituted methane may be substituted with 5-chloro-2(2,4dichlorophenoxy) phenol with substantially similar results.

EXAMPLE 5 Tests of the following shampoo illustrate the improved effectsattributable to the APU resin. This shampoo is effective to inhibit thegrowth of Pityrosporum ovale.

MEL

Triethanolamine lauryl sulfate 10 Lauryldimethyl amine oxide 10Cocornonoethanol amide 5 Ethyl alcohol 10 Zinc Z-pyridinethiol-l-oxide1.6 Resin A"" 2.0 Water Balance "Arninopolyureylcnc resin having amolecular weight of about 4,300 and a repeating unitof{(CH,),N(CH=)(CH=)=N(H)C(O)N(H)+ When the foregoing composition isformulated with a radioactive zinc 2-pyridinethiol-l-oxide (Zn 65)material and is evaluated using the substantivity procedures of Example1, 20.8 micrograms of radioactive zinc 2-pyridinethiol-1-oxide are notedon the gelatin disk. In this evaluation, 2.5 grams of shampoo arediluted with 7.5 grams of water to simulate normal use dilution ofshampoos, and the diluted shampoo is test solution. Under suchconditions, the concentration of zinc 2-pyridinethiol-1-oxide in thetest solution is 0.4 percent by weight, and the concentration of APUresin is 0.5 percent by weight. Repetition of the foregoing test with anidentical composition not containing APU resin results in the depositionof 8.7 micrograms of zinc 2-pyridinethiol-l-oxide. Thus, use of APUresin in combination with zinc Z-pyridinethiol-l-oxide in the presenceof detergents results in an increase in deposition of about percent.

To confirm that increased deposition results in enhanced residualactivity, radioactive disks obtained using the foregoing evaluationtechnique are plated in a standard agar medium inoculated with P. ovale,and the diameters of the zone of inhibition are measured after 24 hoursof incubation. These results are shown in Table I together with resultsof non-radioactive disks. Resin A alone has no zone of inhibition.

Table I Zinc 2 Zone of inhibition pyridinethiol-l-oxide APU resin after24 hours (m.m.)

Radioactive No 249 Radioactive Yes 40.3 Non-radioactive No 20.lNon-radioactive Yes 43.5

The foregoing results indicate that APU resin significantly improves theantibacterial effectiveness of the zinc 2-pyridinethiol-l-oxide.Further, the results show that radioactivity has a minimal effect on theresults.

The effect of APU resin on long-standing activity is illustrated byrepeatedly transferring the radioactivity disks of Table I to freshlyseeded agar plates inoculated with P. ovale for additional incubationperiods after measuring the zone of inhibition. Results are set forth inTable II.

Table 11 Zone of inhibition (m.m.)

APU One Two Three Resin Incubation lncubations lncubations No 24.9 5.8Yes 43.5 24.5 9.4

These results indicate that the presence of APU resin results inimproved antimicrobial effectiveness of the zinc-2-pyridinethiol-l-oxideand longer-lasting effectiveness.

EXAMPLE 6 Example is repeated with the exception that the concentrationof zinc Z-pyridinethiol-l-oxide in the shampoo is reduced to 0.4percent. 17.4 micrograms of zinc 2-pyridinethiol-1-oxide are depositedon the disk. In the absence of the 2 percent of APU resin, 6.1micrograms of zinc Z-pyridinethiol-l-oxide are deposited on the disk.Again, APU resin significantly enhances the deposit of zincZ-pyridinethiol-l -oxide on a proteinaceous substrate.

EXAMPLE 7 The following liquid detergent composition is an effectiveantimicrobial detergent.

Sodium lauryl triethenoxy ether sulfate 8.0

Lauryl dimethyl amine oxide 7.5

Sodium Z-pyridinethiol-l-oxide 2.0

Resin A 1.0

Water Balance When the composition is formulated with radioactive sodium2-pyridinethio1-1-oxide, the zone of inhibition determined as describedin Example 5, the gelatin disk exhibits a halo diameter of 54.2 mm. whentested against P. ovale. In the absence of APU resin, a halo diameter of37.5 m.m. is observed. These results show that APU resin improves theeffectiveness of the watersoluble sodium Z-pyridinethiol-l-oxidematerial as well as the water-insoluble zinc-2-pyridinethiol-l oxide.

EXAMPLE 8 Another antimicrobial liquid detergent composition having a pHof 8.2 follows.

% by weight Cocoamidopropyl dimethyl betaine 22.4 Sodium N-(2hydroxyhexadecyl) methyl taurate 6.0 Sodium hexylbenzene sulfonate 0.8Lauryl dimethyl amine oxide 06 Tribromosalicylanilide 1.0 Resin A 3.0Water Balance Coco corresponds to the mixture of zilkyls derived from amiddle cut of coconut oil. that is, 1% C C 27% C and 7% C When theforegoing composition is formulated with a radioactive (C-l4 tagged)tribromosalicylanilide and the deposition evaluated as described inExample 1, 1.5 micrograms of antibacterial agent are noted on thegelatin disk. As only 0.5 micrograms are deposited in the absence of theAPU resin, use of the APU resin increases deposit by 200 percent.

EXAMPLE 9 Substitution of 1 percent of trichlorocarbanilide for thetribromosalicylanilide in the composition of Example 8 yieldssubstantially similar results.

EXAMPLE 10 A lotion shampoo composition exhibiting effectiveness againstP. ovale follows.

When the foregoing shampoo having a pH of 8.8 is formulated withradioactive 5,7-diiodo-8- hydroxyquinoline (I-l 25) and the depositionevaluated using the procedure of Example 5, the APU resin results in a220 percent increase in the deposition of the antimicrobial agent.Improved depositionis also obtained when the pH of the composition to7.8.

When the concentration of 5,7-diiodo-8- 5 hydroxyquinoline is reduced to1 percent in the composition of Example 10, APU resin achieves a 133percent increase in deposition of that agent.

EXAMPLE 11 The following composition is an improved shampoo composition.

by weight Triethanolamine lauryl sulfate 21 Coconut monoethanolamideTriethanolamine 0.7 Sodium chloride 0.8 Methyl cellulose 09 Ethanol 7.0Resin A 3.0 Fluoroescent agent 1.0 Water Balance When the foregoingcomposition is formulated with the fluorescent agents listed in Table111 and a 1.25% concentration thereof is used to contact a l X 1 inchwool swatch for five minutes, the fluorescent values in Table III areobtained on the wool swatch after it is rinsed with five consecutivel0-milliliter portions of water and air dried.

The foregoing results show that APU resins improve the brighteningeffectiveness of fluorescent agents of the anionic type (stilbenedisulfonate), nonionic (oxazole) and the cationic type (pyrazoline). Theimprovement noted in fluorescent varies from 7 to 200 percent.

EXAMPLE 12 The following composition is an improved conditioningshampoo.

The effectiveness of the aminopolyureylene resin in improving theconditioning properties of the protein is shown by the followingprocedure. A bleached hair tress about 2.5 inches (weight 0.55 grams) isplaced in contact with grams of the shampoo composition of Example 12and the contact is maintained for 30 minutes. The hair tress is thenremoved from the shampoo, subjected to five consecutive rinses with 55milliliters of deionized water each time, air dried, and analyzedspectrophotometrically for hydroxyproline. (Hydroxyproline is an aminoacid found in hydrolyzed protein, but not in hair.) The protein andaminopolyureylene resin are soluble in the shampoo composition having apH of 7.5 and the test results for the composition are set forth inTable IV.

Table lV Protein Protein Resin A Deposited (l by weight by weight byweight 1 Hydroxyproline content expressed as protein. The foregoingtabulation shows that aminopolyureylene resin improves the deposition ofwater-soluble protein onto hair and thereby achieves improvedconditioning effects.

The foregoing tabulation shows that aminopolyureylene resin improves thedeposition of water-soluble protein onto hair and thereby achievesimproved conditioning effects.

Substitution of a benzophenone ultraviolet absorber or a silicone forthe gelatin in Example 12 provides compositions having substantiallysimilar improved effects.

When resins having an average molecular weight in the range of 1,000 to20,000 and a repeating unit of rt g t )t zgg gm p mn-i are substitutedfor the resin in the composition of Example 12, substantially similarresults are obtained.

Other compositions exhibiting improved effectiveness because of thepresence of an aminopolyureylene by weight C to C alkyl* amidopropyldimethyl betaine 16.0 resln thereln follow: Triethanolamine laurylsulfate 4.0 55 Lauryl dimethyl amine oxide 0.5 EXAMPLE l3Polyoxypropylene-polyoxyethylene block copolymer having a hydrophobicmolecular A heavy-duty llquld detergent composition having l of andcomammg 20% by improved resistance to color fading because ofultraviweight of polyoxyethylene 5.0 Condensation product of 1:1 mixtureof ethylene Olet llght WSZ oxide and propylene oxide on butanol 0 (mol.wt. 4,000 2.0 m Resin A q.s. Sodium tridecylbenzene sulfonate 10.0Ethanol 1.9 Potassium xylene sulfonate 8.5 Protein q.s. Lauric-myristicdiethanolamide 4.5 Water, perfume balance Potassium pyrophosphate 15.0

mm) Sodium carboxymethylcellulose 0.5

5 2,4 dihydroxybenzophenone 0.05 'Alkyl group corresponds to the mixtureof alkyls obtained from middle cut of gyqrogAendted Castor on 8' coconutoil esm Water balance Wilson Protein WSP-X250 obtained by enzymatichydrolysis of collagen and having an average molecular weight of about1.000

2,2'hydroxy4,4'dimethoxybenzophenone may be substituted for thebenzophenone in the composition of Example 13 with substantially similarimproved effects.

EXAMPLE 14 A built particulate laundry detergent composition exhibitingimproved antibacterial effectiveness has the following composition:

Fabrics laundered in the foregoing composition exhibit improvedantimicrobial effectiveness.

EXAMPLE 15 A detergent bar composition exhibiting improved resistance tocopper discoloration has the following composition.

1 03 cm OH) on; on

by weight of an aminopolyureylene resin having a molecular weight in therange of 300 to 100,000 and having the following repeating unit: -(CH),,(X)(CH ),,NHC(Y)NH- wherein X is NH,

5 N-C to C alkyl,

Y is O or S and n is 2 or 3; and from 0.05 to 5 percent by weight of anactive material which is an antimicrobial agent selected from the groupconsisting of (A) water-soluble and water-insoluble salts ofZ-pyridinethiol-l-oxide; (B) substituted bisphenols having the formulaOH OH by weight i I Sodium N lauryl B iminodipropionate 8.75 Sodium C toC alkane sulfonate 24.25 R Sodium tallow soap 26.40 I Sodiumtridecylbenzene sulfonate Syrupy phosphoric acid (85%) Stearic Acid n nEifififfi wherein X is halogen, n is l-3, and R is an alkylene of Waterbalance 1 to 4 carbon atoms or divalent sulfur; (C) substituted loomsalicylanilides having the formula Ethylene thiourea may be substitutedfor benzotriaz- O O ole in the composition of Example 15 withsubstantially I g similar results. Y NH" Y While the improved propertiesappear to be due pri- Z Z marily to enhanced deposition and/or retentionof both water-soluble and water-insoluble materials due to the 1presence of the aminopolyureylene resin in the compowherein Y ishydrogen, halogen or trifluoromethyl and sitions, the actual mechanismis not completely under- Stood Accordingly applicant does not wish to beZ is hydrogen or halogen; (D) substituted carbanilides ,having thefollowing structure bound by any particular scientific theory orexplanation.

While compositions containing APU resin and an active material may beprepared by admixing resin and active material in any suitable manner,in the preparation of detergent containing compositions, improvedeffects are obtained when the resin and active material are premixedbefore admixing with the detergent component.

Although the present invention has been described with reference toparticular embodiments and examples, it will be apparent to thoseskilled in the art that similar results may be obtained when the whereinY is hydrogen, halogen or trifluoromethyl, W is halogen or ethoxy and Wis hydrogen or halogen; (E) mono-higher alkyl quaternary ammonium saltsselected from the group consisting of C to C alkyl aminopolyureyleneresin is used in combination with a isoquinonnium halides, 8 to 22 alkylpyridinium wide variety of water-soluble and water-insoluble substancesin addition to those specifically described. hdes and Salts having theformula What is claimed is: R0 l. A detergent composition consistingessentially of i i from 2 to 99 percent by weight of a water-soluble or-R I-T- R A- ganic detergent selected from the group consisting ofanionic, nonionic, amphoteric, zwitterionic, polar nonionic, andcationic detergents; from 0.05 to 5 percent wherein R is C to C alkyl, Rand R are each C to C alkyl, R is C to C alkyl or benzyl, and A isselected from the group consisting of chlorine, bromine, iodine andmethosulfate; (F) 5,7-diiodo-8-hydroxyquinoline; (G)l,6-di-(4-chlorophenyldiguanado) hexane and (H)-chloro-2(2,4-dichlorophenoxy) phenol.

2. A composition in accordance with claim 1 wherein said resin has anaverage molecular weight in the range of 1000 to 20,000 and in saidrepeating unit Y is O and n is 3.

3. A composition in accordance with claim 2 wherein said active materialis zinc pyridinethiol-l-oxide.

4. A composition in accordance with claim 2 wherein said active materialis sodium pyridinethiol-l-oxide.

5. A composition in accordance with claim 2 wherein said active materialis bis(3,5,6-trichloro-2 hydroxyphenyl) methane.

6. A composition in accordance with claim 2 wherein said active materialis cetyl trimethyl ammonium bromide.

7. A composition in accordance with claim 1 wherein said detergent isselected from the group consisting of anionic, amphoteric andzwitterionic detergents and is present in an amount from 10 to 40percent by weight,

said antimicrobial agent is present in an amount from 0.1 to 3 percentby weight, said resin is present in an amount from 0.5 to 3.5 percent byweight, and the balance is primarily water.

8. A composition in accordance with claim 1 wherein said detergent is anon-soap anionic or nonionic detergent and is present in an amount of 5to 20 percent by weight, said antimicrobial agent is present in anamount of 0.1 to 3 percent by weight, said resin is present in an amountof 0.5 to 3.5 percent by weight, and also present is 10 to 25 percent byweight of potassium pyrophosphate, sodium silicate or sodiumnitrilotriacetate and 4 to 12 percent by weight of sodium or potassiumxylene or toluene sulfonate, with the balance being primarily water.

9. A composition in accordance with claim 1 wherein said detergent is anon-soap anionic or nonionic detergent and is present in an amount ofabout 8 to 40 percent by weight, said antimicrobial agent is present inan amount of about 0.1 to 3 percent by weight, said resin is present inan amount of 0.5 to 3.5 percent by weight, and the balance is awater-soluble inorganic or organic builder salt.

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF FROM 2 TO 99PERCENT BY WEIGHT OF WATER-SOLUBLE ORGANIC DETERGENT SELECTED FROM THEGROUP CONSISTING OF ANIONIC, NONIONIC, AMPHOTERIC, ZWITTERIONIC, POLARNONIONIC, AND CATIONIC DETERGENTS, FROM 0.05 TO 5 PERCENT BY WEIGHT OFAN AMINOPOLYUREYLENE RESIN HAVING A MOLECULAR WEIGHT IN THE RANGE OF 300TO 100,000 AND HAVING THE FOLLOWING REPEATING UNIT: ((CH2)N(X)(CH2)NNHC(Y)NH) WHEREIN X IS HN, N-C1 TO C22 ALKYL,
 2. Acomposition in accordance with claim 1 wherein said resin has an averagemolecular weight in the range of 1000 to 20,000 and in said repeatingunit Y is O and n is
 3. 3. A composition in accordance with claim 2wherein said active material is zinc pyridinethiol-1-oxide.
 4. Acomposition in accordance with claim 2 wherein said active material issodium pyridinethiol-1-oxide.
 5. A composition in accordance with claim2 wherein said active material is bis(3,5,6-trichloro-2 hydroxyphenyl)methane.
 6. A composition in accordance with claim 2 wherein said activematerial is cetyl trimethyl ammonium bromide.
 7. A composition inaccordance with claim 1 wherein said detergent is selected from thegroup consisting of anionic, amphoteric and zwitterionic detergents andis present in an amount from 10 to 40 percent by weight, saidantimicrobial ageNt is present in an amount from 0.1 to 3 percent byweight, said resin is present in an amount from 0.5 to 3.5 percent byweight, and the balance is primarily water.
 8. A composition inaccordance with claim 1 wherein said detergent is a non-soap anionic ornonionic detergent and is present in an amount of 5 to 20 percent byweight, said antimicrobial agent is present in an amount of 0.1 to 3percent by weight, said resin is present in an amount of 0.5 to 3.5percent by weight, and also present is 10 to 25 percent by weight ofpotassium pyrophosphate, sodium silicate or sodium nitrilotriacetate and4 to 12 percent by weight of sodium or potassium xylene or toluenesulfonate, with the balance being primarily water.
 9. A composition inaccordance with claim 1 wherein said detergent is a non-soap anionic ornonionic detergent and is present in an amount of about 8 to 40 percentby weight, said antimicrobial agent is present in an amount of about 0.1to 3 percent by weight, said resin is present in an amount of 0.5 to 3.5percent by weight, and the balance is a water-soluble inorganic ororganic builder salt.